1. Field of the Invention
The present invention relates generally to the field of fuel cells, and more specifically, to a simplified direct oxidation fuel cell device containing a direct oxidation fuel cell stack with a fuel container, fuel delivery and reaction product release system.
2. Background Information
Fuel cells are devices in which electrochemical reactions are used to generate electricity. A variety of materials may be suited for use as a fuel depending upon the materials chosen for the components of the cell. Organic materials, such as methanol or natural gas, are attractive choices for fuel due to their high specific energy.
Fuel cell systems may be divided into “reformer-based” systems (i.e., those in which the fuel is processed in some fashion to extract hydrogen from the fuel before it is introduced into the fuel cell system) or “direct oxidation” systems in which the fuel is fed directly into the cell without the need for separate internal or external processing. Most currently available fuel cells are reformer-based fuel cell systems. However, because fuel processing is expensive and requires significant volume, reformer based systems are presently limited to comparatively high power applications.
Direct oxidation fuel cell systems may be better suited for a number of applications in smaller mobile devices (e.g., mobile phones, handheld and laptop computers), as well as in some larger applications. Typically, in direct oxidation fuel cells, a carbonaceous liquid fuel in an aqueous solution (typically aqueous methanol) is applied to the anode face of a membrane electrode assembly (MEA). The MEA contains a protonically-conductive but electronically non-conductive membrane (PCM). Typically, a catalyst which enables direct oxidation of the fuel on the anode is disposed on the surface of the PCM (or is otherwise present in the anode chamber of the fuel cell). Protons (from hydrogen found in the fuel and water molecules involved in the anodic reaction) are separated from the electrons. The protons migrate through the PCM, which is impermeable to the electrons. The electrons thus seek a different path to reunite with the protons and oxygen molecules involved in the cathodic reaction and travel through a load, providing electrical power.
One example of a direct oxidation fuel cell system is a direct methanol fuel cell system or DMFC system. In a DMFC system, methanol in an aqueous solution is used as fuel (the “fuel mixture”), and oxygen, preferably from ambient air, is used as the oxidizing agent. There are two fundamental reactions that occur in a DMFC which allow a DMFC system to provide electricity to power consuming devices: the anodic disassociation of the methanol and water fuel mixture into CO2, protons, and electrons; and the cathodic combination of protons, electrons and oxygen into water. The overall reaction may be limited by the failure of either of these reactions to proceed to completion at an acceptable rate (more specifically, failure to oxidize the fuel mixture will limit the cathodic generation of water, and vice versa). A common problem with DMFCs, is that some methanol may pass through the membrane, from the anode portion of the fuel cell to the cathode chamber of the fuel cell without reacting. This phenomenon, known as methanol crossover, may be limited by introducing a dilute aqueous methanol solution as fuel, rather than a concentrated solution.
Fuel cells and fuel cell systems have been the subject of intensified recent development because of their ability to efficiently convert the energy in carbonaceous fuels into electric power while emitting comparatively low levels of environmentally harmful substances. The adaptation of fuel cell systems to mobile uses, however, is not straight-forward because of the technical difficulties associated with reforming the complex carbonaceous fuels in a simple, cost effective manner, and within acceptable form factors and volume limits. Further, a safe and efficient storage means for substantially pure hydrogen (which is a gas under the relevant operating conditions) presents a challenge because hydrogen gas must be stored at high pressure and at cryogenic temperatures or in heavy absorption matrices in order to achieve useful energy densities. It has been found, however, that a compact means for storing hydrogen is in a hydrogen rich compound with relatively weak chemical bonds, such as methanol or an aqueous methanol solution (and to a lesser extent, ethanol, propane, butane and other carbonaceous liquids or aqueous solutions thereof).
In particular DMFCs are being developed for commercial production for use in portable electronic devices. Thus, the DMFC system, including the fuel cell, and the components may be fabricated using materials that not only optimize the electricity-generating reactions, but which are also cost effective. Furthermore, the manufacturing process associated with those materials should not be prohibitive in terms of labor intensity cost.
A typical MEA includes a centrally disposed protonically conductive, electronically non-conductive membrane (“PCM”). One example of a commercially available PCM is NAFION® (a registered trademark of E.I. Dupont de Nemours and Company), a cation exchange membrane comprised of perflorocarbon polymers with side chain termini of perflourosulfonic acid groups, in a variety of thicknesses and equivalent weight. The PCM is typically coated on each face with an electrocatalyst such as platinum, or platinum/ruthenium mixtures or alloy particles. On either face of the catalyst coated PCM, the electrode assembly typically includes a diffusion layer. The diffusion layer functions to evenly distribute the liquid fuel mixture across the anode in the case of the fuel, or the gaseous oxygen from air or other source across the cathode face of the PCM. In addition, flow field plates are often placed on the surface of the diffusion layers that are not in contact with the coated PCM. The flow field plates function to provide mass transport of the reactants and by products of the electrochemical reactions, and they also have a current collection functionality in that the flow field plates act to collect and conduct electrons to the external wires connecting to the load.
Direct methanol fuel cell systems typically employ an active management scheme to manage the reactants and byproducts in the direct methanol fuel cell including pumping or otherwise causing fuel mixtures, byproducts and reactants to be circulated throughout the fuel cell system. However, actively managing these reactants and byproducts can involve the use of pumps and flow channels or conduits. In a small hand-held device, in which DMFCs have great potential application, parasitic power losses and volume consumed due to pumps and other devices can be relatively large when compared to the overall power output and volume of a small unit. Thus, it is desirable to avoid using extra pumps, valves and components that consume power or occupy volume within the system. Moreover, such additional components can result in a greater manufacturing and production expense, particularly when those products are going to be manufactured in commercial quantities. In addition, the additional complexity involved in active management of the gases and fluids within the system create a bulky system which can present difficulties with conforming with requisite form factors and space constraints associated with small hand-held devices.
It is thus critical to minimize the complexity and volume of such systems and it is also important to reduce the cost and complexity of manufacturing in large-scale production.
In addition to systemic considerations, it is important to maximize the efficiency of the fuel cell by minimizing certain phenomena associated with DMFCs, as known to those skilled in the art. One goal is to minimize undesirable methanol crossover, which occurs where more methanol than necessary is delivered to the anode side of the fuel cell, and passes through to the cathode without producing electricity, thus wasting fuel and generating unnecessary heat. In addition, it is also desirable to avoid a buildup of cathodically generated water on the cathode diffusion layer, in order to prevent flooding of the cathode catalyst, thus halting the cathodic half reaction, resulting in performance losses.
There remains a need for a direct oxidation fuel cell system, which includes the ability to adjust the amount of methanol, which is presented to the anode in order to avoid excessive amounts of unreacted fuel in the cell. In addition, there remains a need for simplified cell geometry and simple mechanisms for flow adjustment to achieve system simplicity and reliability and facilitate large-scale production of such systems for mass manufacturing.
It is thus an object of the present invention to minimize the loss of methanol and water via crossover and carryover by controlling the introduction of those fluids into the system in the first place, and to present a very simple fuel delivery system which increases net power provided to the load due to the minimization of parasitic losses that are suffered in more complex systems with more active flow of liquid(s). This type of passive direct methanol fuel cell system operation is also facilitated by the separation of gaseous carbon dioxide within the fuel cell, thus eliminating the requirement for at least one pump within the DMFC system.